Polyacetal resin composition

ABSTRACT

The present invention provides a polyacetal resin composition comprising (I) a polyacetal resin; and per 100 parts by weight thereof, (II) more than 5 parts by weight but less than 100 parts by weight of calcium carbonate, wherein the calcium carbonate has an average particle diameter of 0.1 to less than 1.5 μm and an average aspect ratio (L/D) which is a ratio of average major axis (L) of particles to average minor axis (D) of particles (D) of 3 or less; (III) 0.00.5 to 10 parts by weight of an organic acid; and (IV) 0 to less than 0.05 part by weight of a fatty acid ester, wherein the amount of Na relative to Ca is 250 ppm or less while the amount of Sr relative to Ca is 500 to 2500 ppm. The resin composition of the invention is excellent in a balance of thermal stability and mechanical properties, such as rigidity and toughness, also excellent in anti-creep life, fatigue resistance and acid resistance, so that it can be suitably used in various fields, such as automobile, electrical/electronic and other industries.

TECHNICAL FIELD

The present invention relates to a polyacetal resin compositioncomprising a polyacetal resin and calcium carbonate having a specificshape and an organic acid and also containing specific amounts of Na andSr, which is excellent in a balance of thermal stability and mechanicalproperties, such as rigidity and toughness, and also excellent inanti-creep life, fatigue resistance and acid resistance.

BACKGROUND ART

Since a polyacetal resin is excellent in a balance of rigidity,strength, toughness, anti-creep life, fatigue resistance, chemicalresistance and sliding properties, heat resistance, and the like and iseasy to process, it is used as an engineering plastic in wide range ofapplications including electric parts, mechanical parts of electricparts, automobile parts, and other mechanical parts as representatives.

In particular, as characteristic applications of the polyacetal resin,it is used for sliding-related parts such as gears and cams inmechanical parts of electric and electronic devices. Parts insliding-related applications, such as gears and cams, are frequentlyused in a state where a certain load is applied to the parts. Asproperties, to say nothing of sliding properties, not only short-termmechanical properties such as rigidity, strength, and toughness but alsolong-term properties such as anti-creep life and fatigue resistance arefrequently required.

Recently, in these parts in sliding-related applications and the like,weight saving, miniaturization, and increase in durability of the partshave been required. As a result, there has been desired a polyacetalresin composition wherein not only short-term mechanical properties suchas rigidity, strength, and toughness but also long-term properties suchas anti-creep life and fatigue resistance are improved.

Thus, as common methods, as in the case of other engineering plasticssuch as polyamides, improvement of its performance has been attempted byblending an inorganic filler such as glass fibers, wollastonite, orcarbon fibers. However, in the case that glass fibers or an inorganicfiller is blended into the polyacetal resin, the blending is effectivefor improvement of mechanical properties such as rigidity and toughnessbut sliding properties originally characteristic of the polyacetal resinand long-term properties such as anti-creep life and fatigue resistanceand further toughness are sometimes severely deteriorated, so that themethod is not effective. Moreover, in the case of blending the glassfibers or an inorganic filler in a large amount, thermal stability ofthe polyacetal resin is sometimes lowered and thus there is apossibility that moldability, heat-resistant aging property, or the likemay be adversely effected, so that the method becomes problematic insome cases.

There have been known polyacetal resin compositions comprising apolyacetal resin and calcium carbonate wherein a saturated fatty acid,an unsaturated fatty acid, or a metal salt thereof is used as aninterfacial adhesion accelerator between the polyacetal resin andcalcium carbonate (e.g., Patent Documents 1 to 3) and a polyacetal resincomposition wherein a specific sulfate compound is used as aninterfacial adhesion accelerator (e.g., Patent Document 4). Thepolyacetal resin compositions are known to be excellent in a balance ofrigidity and toughness and also excellent in thermal stability andsliding properties. Furthermore, polyacetal resin compositionscomprising a polyacetal resin, calcium carbonate, and a specific fattyacid ester are known to be particularly excellent in sliding properties(e.g., Patent Documents 5 and 6).

The above polyacetal resin compositions comprising a polyacetal resinand calcium carbonate have characteristics that they are excellent in abalance of rigidity and toughness and also excellent in slidingproperties and thermal stability as compared with the cases that glassfibers or an inorganic filler is blended into the polyacetal resin.However, in the case of the use as actual structural parts, there is acase that higher rigidity and toughness are required. Moreover, withregard to the increase in durability of the structural parts, long-termproperties such as anti-creep life and fatigue resistance are sometimesinsufficient.

In addition to the above problems, there is a case that improvement ofdurability of the polyacetal resin against an acid, i.e., acidresistance, is required. The acid resistance herein means resistance toweight loss and deterioration in mechanical properties that a moldedarticle of the polyacetal resin suffers from, when being placed under anacidic atmosphere, through corrosion of the molded article per se. As aspecific example, a fuel-feeding unit in automobile parts may bementioned. Hitherto, the polyacetal resin has been used in large-sizedparts which come into direct contact with gasoline, such as fuel pumpmodules, because of the properties of excellent chemical resistance,especially gasoline fuel impermeability. For the purpose of contributingto prevention of recent global warming, there is a trend of activelypopularizing diesel fuel vehicles which less emit carbon dioxide insteadof gasoline fuel vehicles and it is attempted to use the polyacetalresin in fuel-feeding units for diesel fuel. However, since light oil tobe used as diesel fuel contains a high level of sulfur, i.e., a highlevel of sulfur oxides as compared with gasoline fuel and the maximumtemperature for use is higher than the case of gasoline fuel, there is aproblem that parts which come into direct contact with the diesel fuel,e.g., pump modules, fuel valves, fuel tank flanges, fuel level gauges,and the like may be corroded and cannot exhibit a sufficient durabilityas the parts in the case of conventional polyacetal resins.

For the purpose of solving such a problem, there have been disclosed acomposition wherein a hindered phenol-based compound, a specificphosphorus-based stabilizer, a specific nitrogen compound, and aspecific metal hydroxide or alkoxy metal are blended into a polyacetalresin (Patent Document 7), a material wherein an alkaline additive isincorporated into a polyacetal resin base material (Patent Document 8),and a composition comprising a polyacetal resin and also zinc oxide andpolyalkylene glycol (Patent Document 9). As a result, there is atendency that acid resistance may be improved as compared withconventional polyacetal resins but a balance of rigidity and toughnesstends to be disrupted owing to the addition of various additives, sothat a design with a large thickness is required due to insufficiency ofrigidity and toughness in the case of the use as large-sized parts suchas fuel pumps. Moreover, there is a problem that the above materialslack reliability because of insufficient long-term properties such asanti-creep life.

As described above, in various applications, there has been desired apolyacetal composition which is excellent in a balance of thermalstability and mechanical properties, such as rigidity and toughness, andalso excellent in anti-creep life, fatigue resistance and further acidresistance.

Patent Document 1: British Patent Application Publication No. 1123358

Patent Document 2: JP-A-1-170641,

Patent Document 3: JP-T-2004-506772,

Patent Document 4: U.S. Pat. No. 4,456,710,

Patent Document 5: JP-A-1-263145,

Patent Document 6: JP-A-5-51514,

Patent Document 7: Japanese Patent No. 3157579,

Patent Document 8: JP-A-11-302497,

Patent Document 9: JP-A-2001-11284,

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention

An object of the present invention is to provide a polyacetalcomposition which is excellent in a balance of thermal stability andmechanical properties, such as rigidity and toughness, and alsoexcellent in anti-creep life, fatigue resistance and further acidresistance.

Means for Solving the Problems

As a result of extensive studies for solving the above problems, thepresent inventors have found that a polyacetal resin compositioncomprising a polyacetal resin and calcium carbonate having a specificshape and an organic acid and also containing specific amounts of Na andSr is excellent in a balance of thermal stability and mechanicalproperties, such as rigidity and toughness, and also is excellent inanti-creep life, fatigue resistance and acid resistance. Thus, they haveaccomplished the invention.

Namely, the invention is as follows:

(1) A polyacetal resin composition comprising:

(I) a polyacetal resin; and per 100 parts by weight thereof,

(II) more than 5 parts by weight but less than 100 parts by weight ofcalcium carbonate, wherein the calcium carbonate has an average particlediameter of from 0.1 μm to less than 1.5 μm and an average aspect ratio(L/D) which is a ratio of average major axis (L) of particles to averageminor axis (D) of particles of 3 or less;

(III) 0.005 to 10 parts by weight of an organic acid; and

(IV) 0 to less than 0.05 parts by weight of a fatty acid ester,

wherein the amount of Na relative to Ca is 250 ppm or less and theamount of Sr relative to Ca is from 500 to 2500 ppm;

(2) The polyacetal resin composition according to the above (1), whereinthe amount of Na relative to Ca in the composition is 100 ppm or less;

(3) The polyacetal resin composition according to the above (1) or (2),wherein the amount of Sr relative to Ca in the composition is from 600to 1500 ppm;

(4) The polyacetal resin composition according to any one of the above(1) to (3), wherein formaldehyde-generating rates, at the time when thepolyacetal resin (I) is heated at 220° C. under an argon stream, forheating periods of from 2 minutes to 10 minutes, from 10 minutes to 30minutes and from 50 minutes to 90 minutes are each 15 ppm/min or less;

(5) The polyacetal resin composition according to any one of the above(1) to (4), wherein the polyacetal resin (I) is a heat-stabilizedpolyacetal resin obtained by treating to stabilize thermally unstableterminals with at least one quaternary ammonium compound represented bythe following formula:[R¹R²R³R⁴N⁺]_(n)X^(−n)wherein R¹, R², R³, R⁴ each independently represents an unsubstituted orsubstituted alkyl group having 1 to 30 carbon atoms, an aryl grouphaving 6 to 20 carbon atoms, an aralkyl group in which an unsubstitutedor substituted alkyl group having 1 to 30 carbon atoms is substitutedwith at least one aryl group having 6 to 20 carbon atoms, or analkylaryl group in which an aryl group having 6 to 20 carbon atoms issubstituted with at least one unsubstituted or substituted alkyl grouphaving 1 to 30 carbon atoms, provided that the unsubstituted orsubstituted alkyl group may be any of linear, branched or cyclic, andthat in the unsubstituted alkyl group, aryl group, aralkyl group oralkylaryl group, hydrogen atom(s) may be substituted with halogen(s); nrepresents an integer of 1 to 3; and X represents a hydrogen atom, or anacid residue of a carboxylic acid having 1 to 20 carbon atoms, ahydroacid, an oxo acid, an inorganic thio acid or an organic thio acidhaving 1 to 20 carbon atoms;

(6) The polyacetal resin composition according to any one of the above(1) to (5), wherein the polyacetal resin (I) is a copolymer having amelting point of 164 to 172° C.;

(7) The polyacetal resin composition according to any one of the above(1) to (6), wherein the calcium carbonate (II) is light calciumcarbonate;

(8) The polyacetal resin composition according to any one of the above(1) to (7), wherein the calcium carbonate (II) has an average particlediameter of from 0.1 μm to 1.0 μm;

(9) The polyacetal resin composition according to any one of the above(1) to (8), wherein the calcium carbonate (II) has a content ofparticles having a particle diameter of 1 μm or less of 90% or more;

(10) The polyacetal resin composition according to any one of the above(1) to (9), wherein the calcium carbonate (II) has a BET specificsurface area of from 10 to 200 m²/g;

(11) The polyacetal resin composition according to any one of the above(1) to (10), wherein the calcium carbonate (II) comprises sphericalparticles, cubic particles, rectangular particles, amorphous particles,or a mixture thereof;

(12) The polyacetal resin composition according to any one of the above(1) to (11), wherein the organic acid (III) is a saturated fatty acidhaving 8 to 36 carbon atoms;

(13) The polyacetal resin composition according to any one of the above(1) to (12), wherein the fatty acid ester (IV) is an ester of a fattyacid having 10 to 24 carbon atoms with a monohydric or polyhydricalcohol having 2 to 22 carbon atoms;

(14) A polyacetal resin composition comprising the polyacetal resincomposition according to any one of the above (1) to (13) and further(V) 0.1 to 10 parts by weight of a polyalkylene glycol per 100 parts byweight of the polyacetal resin composition;

(15) The polyacetal resin composition according to the above (14),wherein the polyalkylene glycol (V) is polyethylene glycol orpolypropylene glycol;

(16) The polyacetal resin composition according to the above (14) or(15), wherein the polyalkylene glycol (V) has a number-average molecularweight of from 10,000 to 45,000;

(17) A process for producing a polyacetal resin composition comprising astep of simultaneously melt-kneading:

(I) a polyacetal resin; and per 100 parts by weight thereof,

(II) more than 5 parts by weight but less than 100 parts by weight ofcalcium carbonate which has an average particle diameter of from 0.1 μmto less than 1.5 μm and an average aspect ratio (L/D) which is a ratioof average major axis (L) of particles to average minor axis (D) ofparticles of 3 or less and which is not surface-treated with a saturatedfatty acid, unsaturated fatty acid and a metal salt thereof having 8 to32 carbon atoms; and

(III) 0.005 to 10 parts by weight of an organic acid,

at melting point of the polyacetal resin (I) or higher;

(18) The process according to the above (17), whereinformaldehyde-generating rates, at the time when the polyacetal resin (I)is heated at 220° C. under an argon stream, for heating periods of from2 minutes to 10 minutes, from 10 minutes to 30 minutes and from 50minutes to 90 minutes are each 15 ppm/min or less;

(19) The process according to the above (17) or (18), wherein thepolyacetal resin (I) is a heat-stabilized polyacetal resin obtained bytreating to stabilize thermally unstable terminals with at least onequaternary ammonium compound represented by the following formula:[R¹R²R³R⁴N⁺]_(n)X^(−n)wherein R¹, R², R³, R⁴ each independently represents an unsubstituted orsubstituted alkyl group having 1 to 30 carbon atoms, an aryl grouphaving 6 to 20 carbon atoms, an aralkyl group in which an unsubstitutedor substituted alkyl group having 1 to 30 carbon atoms is substitutedwith at least one aryl group having 6 to 20 carbon atoms, or analkylaryl group in which an aryl group having 6 to 20 carbon atoms issubstituted with at least one unsubstituted or substituted alkyl grouphaving 1 to 30 carbon atoms, provided that the unsubstituted orsubstituted alkyl group may be any of linear, branched or cyclic, andthat in the unsubstituted alkyl group, aryl group, aralkyl group oralkylaryl group, hydrogen atom(s) may be substituted with halogen(s); nrepresents an integer of 1 to 3; and X represents a hydrogen atom, or anacid residue of a carboxylic acid having 1 to 20 carbon atoms, ahydroacid, an oxo acid, an inorganic thio acid or an organic thio acidhaving 1 to 20 carbon atoms;

(20) The process according to any one of the above (17) to (19), whereinthe polyacetal resin (I) is a copolymer having a melting point of 164 to172° C.;

(21) The process according to any one of the above (17) to (20), whereinin the calcium carbonate (II), the amount of Na relative to Ca is 250ppm or less and the amount of Sr relative to Ca is from 500 to 2500 ppm;

(22) The process according to any one of the above (17) to (21), whereinthe calcium carbonate (II) is light calcium carbonate;

(23) The process according to any one of the above (17) to (22), whereinthe calcium carbonate (II) has an average particle diameter of is from0.1 μm to 1.0 μm;

(24) The process according to any one of the above (17) to (23), whereinthe calcium carbonate (II) has a content of particles having a particlediameter of 1 μm or less of 90% or more;

(25) The process according to any one of the above (17) to (24), whereinthe calcium carbonate (II) has a BET specific surface area of from 10 to200 m²/g;

(26) The process according to any one of the above (17) to (25) whereinthe calcium carbonate (II) comprises spherical particles, cubicparticles, rectangular particles, amorphous particles, or a mixturethereof;

(27) The process according to any one of the above (17) to (26), whereinthe organic acid (III) is a saturated fatty acid having 8 to 36 carbonatoms.

ADVANTAGES OF THE INVENTION

The polyacetal resin composition of the invention exhibits advantagesthat it is excellent in a balance of thermal stability and mechanicalproperties, such as rigidity and toughness, and also excellent inanti-creep life, fatigue resistance and acid resistance.

BEST MODE FOR CARRYING OUT THE INVENTION

The following will explain the present invention specifically.

The polyacetal resin (I) for use in the invention is a known polyacetalresin and is not particularly limited. Examples thereof include apolyacetal homopolymer substantially solely consisting of oxymethyleneunits obtained by homopolymerization of formaldehyde monomer or a cyclicoligomer of formaldehyde, such as trimer (trioxane) or tetramer(tetraoxane) thereof, and a polyacetal copolymer obtained bycopolymerization of formaldehyde monomer or a cyclic oligomer offormaldehyde, such as trimer (trioxane) or tetramer (tetraoxane)thereof, with a cyclic ether or a cyclic formal, such as ethylene oxide,propylene oxide, epichlorohydrin, 1,3-dioxolane, or a cyclic formal of aglycol or diglycol including 1,4-butandiol formal. Among the polyacetalcopolymers, in view of an excellent balance of rigidity, toughness, andheat resistance, preferred amount of a comonomer such as 1,3-dioxolaneto be added is from 0.1 to 60 mol %, more preferably from 0.1 to 20 mol,most preferably from 0.15 to 10 mol relative to 1 mol of trioxane. Atthis time, the melting point of the polyacetal resin depends on theamount of the comonomer and is preferably from 164° C. to 172° C., morepreferably from 165° C. to 171° C., most preferably from 167° C. to 170°C.

Moreover, as a polyacetal copolymer, use can be also made of a branchedpolyacetal copolymer having branching obtained by copolymerization of amonofunctional glycidyl ether or a crosslinked polyacetal copolymerhaving a crosslinked structure obtained by copolymerization of apolyfunctional glycidyl ether. Furthermore, use can be also made of acompound having a functional group such as hydroxyl group at bothterminals or one terminal, e.g., a block polyacetal homopolymer obtainedby polymerization of formaldehyde monomer or a cyclic oligomer offormaldehyde in the presence of a polyalkylene glycol or a compoundhaving a functional group such as hydroxyl group at both terminals orone terminal, e.g., a block polyacetal copolymer having block componentsobtained by copolymerization of formaldehyde monomer or a cyclicoligomer of formaldehyde, such as trimer (trioxane) or tetramer(tetraoxane) thereof, with a cyclic ether or a cyclic formal in thepresence of hydrogenated polybutadiene glycol. In the invention, theabove polyacetal resin may be used singly or as a mixture of two or morethereof.

Among the above polyacetal resins, in view of an excellent balance ofrigidity, toughness, and thermal stability, as the polyacetal resin (I),a random-type polyacetal copolymer wherein the comonomer components arerandomly combined, a block-type polyacetal copolymer, a branched typepolyacetal copolymer, or a crosslinked polyacetal copolymer and amixture thereof are preferred. Moreover, in view of cost, a random-typepolyacetal copolymer or block-type polyacetal copolymer is morepreferred.

Furthermore, in view of thermal stability, as the polyacetal resin (I),when it is heated at 220° C. under an argon stream,formaldehyde-generating rates for heating periods of from 2 minutes to10 minutes, from 10 minutes to 30 minutes, and from 50 minutes to 90minutes are each preferably 15 ppm/min. or less, more preferably 10ppm/min. or less, most preferably 5 ppm/min. or less. The followingspecifically describes the measurement of the aboveformaldehyde-generating rate. Under a nitrogen stream (50 NL/hr), thepolyacetal resin is heated to melt at 220° C., formaldehyde generated isabsorbed in water, and then is titrated by a sodium sulfite method. Atthat time, when the amount (ppm) of formaldehyde generated from thestart of heating until 2 minutes has passed Y₁₀, taken as Y₂, the amountuntil 10 minutes has passed as Y₁₀, the amount until 30 minutes haspassed as Y₃₀, the amount until 50 minutes has passed as Y₅₀, and theamount until 90 minutes has passed as Y₉₀, the rates are calculated asfollows:

Generating rate from 2 minutes to 10 minutes: (Y₁₀−Y₂)/8 (ppm/min.),

Generating rate from 10 minutes to 30 minutes: (Y₃₀−Y₁₀)/20 (ppm/min.),and

Generating rate from 50 minutes to 90 minutes: (Y₉₀−Y₅₀)/40 (ppm/min.).These values are derived from the formaldehyde attached to thepolyacetal resin, derived from the formaldehyde generated bydecomposition of terminals of the polyacetal resin, and derived from theformaldehyde generated by decomposition of main chain of the polyacetalresin, respectively. The smaller these values are, the more excellentthe thermal stability is.

Melt floor index MFI of the above polyacetal resin (I) (measuredaccording to ASTM-D1238) is not particularly limited but is preferablyfrom 0.1 g/10 minutes to 150 g/10 minutes, more preferably from 0.5 g/10minutes to 130 g/10 minutes, most preferably 1 g/10 minutes to 100 g/10minutes in view of processability.

In the invention, the process for producing the polyacetal resin (I) maybe a known process for producing a polyacetal resin and is notparticularly limited. For example, in the case of the above polyacetalhomopolymer, there may be mentioned a process wherein highly pureformaldehyde is introduced into an organic solvent containing an organicamine, an organic or inorganic tin compound, a basic polymerizationcatalyst such as a metal hydroxide to polymerize and, after filtrationof the polymer, it is heated in acetic anhydride in the presence ofsodium acetate to acetylate the polymer terminals. Moreover, in the caseof the above polyacetal copolymer, there may be mentioned a productionprocess wherein highly pure trioxane and copolymerization component(s)such as ethylene oxide and/or 1,3-dioxolane, and a chain transfer agentfor molecular weight control are introduced into an organic solvent suchas cyclohexane, cationic polymerization is conducted using apolymerization catalyst such as a Lewis acid like boron trifluoridediethyl ether complex, and then deactivation of the catalyst andstabilization of terminal groups are effected or a production processwherein bulk polymerization is conducted by introducing trioxane,copolymerization component(s), a chain transfer agent for molecularweight control, and a catalyst into a self cleaning-type extrusionkneader such as a co-kneader, a twin-screw continuous extrusion kneader,or a twin paddle-type continuous mixer and then a quaternary ammoniumcompound such as choline hydroxide formate is further added to removeunstable terminals by decomposition.

As a method of obtaining a preferred polyacetal resin (I) excellent inthermal stability, there may be mentioned a method of stabilizing apolyacetal resin by treating thermally unstable terminals with at leastone quaternary ammonium compound represented by the following formula:[R¹R²R³R⁴N⁺]_(n)X^(−n)wherein R¹, R², R³, R⁴ each independently represents an unsubstituted orsubstituted alkyl group having 1 to 30 carbon atoms, an aryl grouphaving 6 to 20 carbon atoms, an aralkyl group in which an unsubstitutedor substituted alkyl group having 1 to 30 carbon atoms is substitutedwith at least one aryl group having 6 to 20 carbon atoms, or analkylaryl group which an aryl group having 6 to 20 carbon atoms issubstituted with at least one unsubstituted or substituted alkyl grouphaving 1 to 30 carbon atoms, provided that the unsubstituted orsubstituted alkyl group may be any of linear, branched, or cyclic, andthat in the unsubstituted alkyl group, aryl group, aralkyl group oralkylaryl group, hydrogen atom(s) may be substituted with halogen(s); nrepresents an integer of 1 to 3; and X represents a hydrogen atom, or anacid residue of a carboxylic acid having 1 to 20 carbon atoms, ahydroacid, an oxo acid, an inorganic thio acid or an organic thio acidhaving 1 to 20 carbon atoms.

In the above general formula, preferred R¹, R², R³, and R⁴ areindependently an alkyl group having 1 to 5 carbon atoms or ahydroxyalkyl group having 2 to 4 carbon atoms, and furthermore it ismore preferable that at least one of R¹, R², R³, and R⁴ is ahydroxyethyl group. Specific examples of R¹, R², R³, and R⁴ includehydroxides of tetramethylammonium, tetraethylammonium,tetrapropylammonium, tetra-n-butylammonium, cetyltrimethylammonium,tetradecyltrimethylammonium, 1,6-hexamethylene-bis(trimethylammonium),decamethylene-bis(trimethylammonium)trimethyl-3-chloro-2-hydroxypropylammonium,trimethyl(2-hydroxyethyl)ammonium, triethyl(2-hydroxyethyl)ammonium,tripropyl(2-hydroxyethyl)ammonium, tri-n-butyl(2-hydroxyethyl ammonium,trimethylbenzylammonium, triethylbenzylammonium,tripropylbenzylammonium, tri-n-butylbenzylammonium,trimethylphenylammonium, triethylphenylammonium,trimethyl-2-oxyethylammonium, monomethyltrihydroxyethylammonium,monoethyltrihydroxyethylammonium, octadecyl(2-hydroxyethyl)ammonium,tetrakis(hydroxyethyl)ammonium, etc.; salts of hydroacids such ashydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.; salts ofoxo acids such as sulfuric acid, nitric acid, phosphoric acid, carbonicacid, boric acid, chloric acid, iodic acid, silicic acid, perchloricacid, chlorous acid, hypochlorous acid, chlorosulfuric acid,amidosulfuric acid, disulfuric acid, tripolyphosphoric acid, etc.; saltsof thio acids such as thiosulfuric acid; salts of carboxylic acids suchas formic acid, acetic acid, propionic acid, butanoic acid, isobutyricacid, pentanoic acid, capronic acid, caprylic acid, capric acid, benzoicacid, oxalic acid, etc.; or the like. Among them, hydroxides and saltsof sulfuric acid, carbonic acid, boric acid, and carboxylic acids arepreferred. Among carboxylic acids, formic acid, acetic acid, andpropionic acid are particularly preferred. These quaternary ammoniumcompounds can be used alone or in combination of two or more thereof.

An amount of the quaternary ammonium compound to be added is from 0.05to 50 ppm by weight, preferably from 1 to 30 ppm by weight in terms ofthe amount of nitrogen originating from the quaternary ammonium compoundrepresented by the following formula on the basis of total weight of thepolyacetal resin and the quaternary ammonium compound.P×14/Qwherein P represents a concentration of the quaternary ammonium compoundrelative to the polyacetal resin (ppm by weight); “14” is the atomicweight of nitrogen; and Q represents the molecular weight of quaternaryammonium compound.

When the amount of the quaternary ammonium compound added is less than0.05 ppm by weight, the decomposition rate of the unstable terminalgroups tends to be lowered and when it exceeds 50 ppm by weight, colortone of the polyacetal resin resulting from the decomposition of theunstable terminal groups tends to be deteriorated.

As a method of the above stabilization, the above quaternary ammoniumcompound and the polyacetal resin is preferably subjected to heattreatment at a resin temperature of from the melting point of thepolyacetal resin to 260° C. using an extruder, a kneader, or the like.Above 260° C., there will be a coloring problem and a problem ofdecomposition of polymer main chain (formation of low molecular weightpolymers). Moreover, a method of adding the quaternary ammonium compoundis not particularly limited. That is, a method of adding it as anaqueous solution in the step of deactivating the polymerizationcatalyst, a method of spraying it onto the resin powder, and the likeare available. Any of these methods can be used, so long as thequaternary ammonium compound is present in the step of heat treatment ofthe polyacetal resin. The compound may be injected into an extruder orthe compound is attached to resin pellets and the decomposition of theunstable terminals may be carried out in the successive blending step.The decomposition of the unstable terminals can be carried out after thepolymerization catalyst in the polyacetal resin obtained bypolymerization is deactivated or can be carried out without deactivatingthe polymerization catalyst.

The calcium carbonate (II) for use in the invention is not particularlylimited so long as the average particle diameter is from 0.1 μm to lessthan 1.5 μm and the average aspect ratio (L/D) which is a ratio ofaverage major axis (L) of the particle to average minor axis (D) of theparticle is 3 or less. For example, the crystalline form of the calciumcarbonate may be any of calcite, aragonite, and vaterite, which aregenerally known. Moreover, in view of the production method and kind,the calcium carbonate may be naturally occurring heavy calcium carbonateor light calcium carbonate (sometimes referred to as colloidal calciumcarbonate, precipitated calcium carbonate, active calcium carbonate, orthe like). They may be used singly or as a mixture of two or morethereof so long as their properties fall within the above range.

With regard to the calcium carbonate (II) for use in the invention, fromthe viewpoints that it has appropriate wettability, compatibility, andadhesiveness with the polyacetal resin and is excellent indispersibility and a balance of mechanical properties and anti-creeplife and fatigue resistance of the resulting polyacetal resin areexcellent, light calcium carbonate may be mentioned as preferred calciumcarbonate and also calcite is preferred as the crystalline form. On thisoccasion, the shape of the calcium carbonate is spherical one, cubicone, rectangular one, spindle-shaped one, amorphous one, or the like butpreferred shape is spherical one, cubic one, rectangular one, amorphousone, or a mixture thereof. Moreover, the average particle diameter ofthe calcium carbonate is preferably from 0.1 to 1.0 μm, more preferablyfrom 0.1 to 0.6 μm, most preferably from 0.10 to 0.40 μm. Furthermore,the average aspect ratio (L/D) which is a ratio of average major axis(L) of the particle to average minor axis (D) of the particle ispreferably 3 or less, more preferably 2 or less, most preferably 1.5 orless. In the invention, in the shade of the particles of calciumcarbonate, the shortest distance between two parallel lines tangent tooutline in a plane view of the particle is referred to as minor axis andthe largest distance between parallel lines perpendicular to the aboveparallel lines is referred to as major axis using the definition ofHeywood. Moreover, the average particle diameter, average major axis,average minor axis, and average aspect ratio are used with defining as:Average particle diameter average major axis=ΣL _(i) ² N _(i) /ΣL _(i) N_(i)Average minor axis=Σd _(i) ² N _(i) /Σd _(i) N _(i)Average aspect ratio L/d=(ΣL _(i) ² N _(i) /ΣL _(i) N _(i))/(Σd _(i) ² N_(i) /Σd _(i) N _(i))when Ni particles of calcium carbonate having a major axis of L_(i) anda minor axis of d_(i) are present in a unit volume. More specifically,calcium carbonate to be investigated using a scanning electronmicroscope (SEM) is sampled, particle image is photographed with amagnification of 1000 to 50000 using it, and each length of at least 100particles of calcium carbonate randomly selected is measured anddetermined.

For the same reason, with regard to the average particle diameter ofpreferred calcium carbonate, the content of particles having a particlediameter of 1 μm or less is 90% or more, more preferably 95% or more,and most preferably 98% or more. The method of measuring the averageparticle diameter is obtained by a light-transmission particle sizeanalyzing method.

For the same reason, the specific surface area of the calcium carbonate(II) is preferably from 10 to 200 m²/g, more preferably from 10 to 100m²/g, most preferably from 10 to 50 m²/g in accordance with a BETadsorption method. The BET method herein is effected according to anitrogen gas adsorption method.

In the polyacetal resin composition of the invention, the amount of Naand the amount of Sr relative to Ca are 250 ppm or less and from 500 to2500 ppm, respectively. These Na and Sr are derived from impuritiescontained in the calcium carbonate (II). In general, with regard tocalcium carbonate, a method of pulverizing and purifying naturallyoccurring heavy calcium carbonate, a method of artificial synthesis ofintroducing carbon dioxide gas into an aqueous calcium hydroxidesolution, purification, and optional addition of an aggregationinhibitor and/or a surface-treating agent, and the like have been known.In any of the steps, Na contained in water or the like and Srreplaceable with Ca may be sometimes incorporated as impurities incalcium carbonate. Moreover, they may be sometimes contained inlimestone or the like used as a raw material of calcium carbonate. Whenthe content of Na and Sr relative to Ca in the invention falls withinthe above range, the resulting polyacetal resin composition is excellentin a balance of thermal stability and mechanical properties, such asrigidity and toughness, also excellent in anti-creep life and fatigueresistance. The reasons thereof are not clear but it is presumed that aneffect of decreasing particle diameter of calcium carbonate andsharpening particle size distribution is present and also wettabilityand interface with the polyacetal resin are improved. For the abovereasons, the amount of Na relative to Ca in the calcium carbonate (II)is preferably 250 ppm or less, more preferably 200 ppm or less, evenpreferably 150 ppm or less, most preferably 100 ppm or less. Similarly,the amount of Sr relative to Ca is preferably from 500 to 2500 ppm, morepreferably from 600 to 1500 ppm, even more preferably from 700 to 1300ppm, most preferably from 800 to 1000 ppm. The above amounts of Na andSr relative to Ca can be determined by a high-frequencyinductively-coupled plasma (IPC) emission spectrometry. Morespecifically, 0.5 g of calcium carbonate is weighed in a platinum dishand carbonized in an electric furnace at 500° C. After cooling, 5 mL ofhydrochloric acid and 5 mL of pure water are added thereto and the wholeis boiled to dissolve on a heater. After cooling, pure water is added toadjust the concentration to a measurable level and quantitativedetermination is carried out by a high-frequency inductively-coupledplasma (IPC) emission spectrometry using IRIS/IP manufactured by ThermoJarrell Ash based on a characteristic wavelength of each metal.Thereafter, the amounts of Na and Sr relative to Ca are calculated.

With regard to the calcium carbonate (II) for use in the invention, forthe purpose of preventing aggregation of particles, a knownsurface-treating agent, a deposition agent, or a complexing agent, andfurther an aggregation inhibitor may be added thereto in a step ofseparating calcium carbonate from a calcium carbonate slurry in theprocess for producing calcium carbonate, particularly in the process forproducing light calcium carbonate and, as a result, the surface thereofmay be treated with the substance. As the surface-treating agent, adeposition agent, or a complexing agent, and an aggregation inhibitor,use can be made of anionic surfactants, cationic surfactants, amphotericsurfactants, nonionic surfactants, as described in, e.g.,“Bunsan/Gyoushu no Kaimel to Ohyo Gijutsu, 1992” (supervised by FumioKitahara, published by K.K. Techno System), pp. 232 to 237. In addition,there may be mentioned silane-coupling agents such as aminosilanes andepoxysilanes, titanate-based coupling agents, and also fatty acids(saturated fatty acids, unsaturated fatty acids), alicyclic carboxylicacids, as well as resin acids and metal soaps.

In the polyacetal resin composition of the invention, from theviewpoints that it is more excellent in a balance of mechanicalproperties, such as rigidity and toughness, and is excellent inanti-creep life, the calcium carbonate (II) contains the abovesurface-treating agent, deposition agent, or complexing agent, andfurther aggregation inhibitor in an amount of preferably less than 3.0%by weight, more preferably less than 1.0% by weight, even morepreferably less than 0.5% by weight, and they are most preferablysubstantially not added. Among them, the calcium carbonate which is nottreated with a saturated fatty acid or unsaturated fatty acid having 8to 32 carbon atoms and a metal salt thereof exhibits an effect ofexcellent anti-creep life and hence is particularly preferred.

The quantitative determination of the above surface-treating agent,deposition agent, or complexing agent, and further aggregation inhibitorcan be confirmed by a thermogravimetry (TGA). Specifically, the calciumcarbonate is loaded on a themogravimeter (TGA), heated to 100° C. at arate of 100° C./minute, subjected to heat treatment at that temperaturefor 10 minutes to remove moisture of the calcium carbonate, and thenheated to 550° C. at a rate of 100° c./minute and subjected to heattreatment at that temperature for 60 minutes. Thereafter, it can bedetermined according to the expression: the amount of the above organiccomponent=[(weight after completion of heat treatment at 100° C. for 10minutes)−(weight after completion of heat treatment at 550° C. for 60minutes)]/(weight after completion of heat treatment at 100° C. for 10minutes)×100 (%).

The addition of the above surface-treating agent and the like to theinorganic filler generally tends to improve dispersibility into theresin and realize excellent mechanical properties, and hence isconsidered preferable. However, with regard to the fine calciumcarbonate for use in the invention, in the production steps of the finecalcium carbonate, the addition of the above surface-treating agent andthe like in an amount more than necessary amount tends to result inincrease in bulk density of the particle, flying in the air at handling,or contrary tight aggregation of the particles. Therefore, theresometimes arise problems that working environment becomes worse at theproduction of the polyacetal resin composition, operations take muchtime and labor, and the like. Furthermore, at the production of thepolyacetal resin composition using melt-kneading, quantitative feedingto a melt kneader becomes difficult and thus there sometimes arises aproblem from the viewpoint of quality of the resulting polyacetal resincomposition. According to the invention, such problems are solved andpreferred dispersion of calcium carbonate into the polyacetal resincomposition can be achieved without substantial use of the abovesurface-treating agent and the like. In addition, the interface has anappropriate wettability and adhesiveness and the resulting polyacetalresin composition is excellent in a balance of mechanical properties,such as rigidity and toughness, and further particularly excellent inanti-creep life.

The organic acid (III) for use in the invention means a monobasic orpolybasic carboxylic acid having an aliphatic group or an aromatic groupand one wherein a substituent such as a hydroxyl group is introducedinto part of them, or an acid anhydride of these acids, a monobasic orpolybasic sulfonic acid having an aliphatic group or an aromatic groupand one wherein a substituent such as a hydroxyl group is introducedinto part of them, or further, a monobasic or polybasic phosphoric acidhaving an aliphatic group or an aromatic group and one wherein asubstituent such as a hydroxyl group is introduced into part of them,and is not particularly limited so long as it is known. For example,there may be mentioned acetic acid, propionic acid, butyric acid,valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid,myristic acid, palmitic acid, heptadecylic acid, stearic acid, pivalicacid, isobutyric acid, and ethylenediaminetetraacetic acid as saturatedfatty acids; oleic acid, elaidic acid, erucic acid, linoleic acid,ricinoleic acid, and the like as unsaturated fatty acids; naphthenicacid and the like as alicyclic carboxylic acids; abietic acid, pimaricacid, palustric acid, neoabietic acid, and the like as resin acids;furthermore, acid anhydrides thereof; laurylsulfonic acid,polyoxyethylenelauryl-ether-sulfonic acid, dodecylbenzenesulfonic acid,dialkylsulfosuccinic acids, and the like as monobasic or polybasicsulfonic acids. They may be used singly or as a mixture of two or morethereof.

Among them, in view of thermal stability and color tone, saturated fattyacids, unsaturated fatty acids, alicyclic carboxylic acids, and resinacids, which are monobasic or polybasic carboxylic acids, can bepreferably mentioned. Moreover, in view of dispersibility into thepolyacetal resin and more excellent color tone, saturated fatty acidsare preferred. Furthermore, with regard to the resulting polyacetalresin composition, in view of bleeding of the carboxylic acid onto thesurface of molded articles or contamination of organic substancesattached to the mold, saturated fatty acids having 8 to 36, morepreferably 10 to 30, most preferably 12 to 24 carbon atoms arepreferred. For example, there may be mentioned lauric acid, tridecylicacid, myristic acid, pentadecylic acid, palmitic acid, heptadecylicacid, stearic acid, nonadecanoic acid, alginic acid, behenic acid,lignoceric acid, cerotic acid, heptacosanoic acid, montanic acid,linoleic acid, alginic acid, and the like.

The fatty acid ester (IV) for use in the invention is a known fatty acidester obtained by polycondensation of a monohydric or polyhydric alcoholwith a fatty acid and is not particularly limited. Examples of themonohydric or polyhydric alcohol include octyl alcohol, capryl alcohol,nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecylalcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecylalcohol, stearyl alcohol, oleyl alcohol, nonadecyl alcohol, eicosylalcohol, behenyl alcohol, ceryl alcohol, melissyl alcohol,2-hexyldecanol, 2-octyldodecanol, 2-decyltetradecanol, unilin alcohol,ethylene glycol, diethylene glycol, triethylene glycol, propylene glycoldipropylene glycol, butanediol, pentanediol, hexanediol, glycerin,diglycerin, triglycerin, threitol, erythritol, pentaerythritol,arabitol, ribitol, xylitol, sorbit, sorbitan, sorbitol, and mannitol. Asthe fatty acid, a saturated fatty acid or an unsaturated fatty acid maybe mentioned. Specifically, there may be mentioned capric acid, lauricacid, myristic acid, palmitic acid stearic acid, 12-hydroxystearic acid,alginic acid, behenic acid, lignoceric acid, cerotic acid, montanicacid, melissic acid, ceroplastic acid, undecylenic acid, oleic acid,elaidic acid, cetoleic acid, erucic acid, brassdic acid, sorbic acidlinoleic acid, linolenic acid, arachidonic acid, propiolic acid,stearolic acid, and the like. More specifically, there may be mentionedglycerin monopalmitate, glycerin dipalmitate, glycerin tripalmitate,glycerin monostearate, glycerin distearate, glycerin tristearate,glycerin monobehenate, glycerin dibehenate, glycerin tribehenate,glycerin monomontanate, glycerin dimontanate, glycerin trimontanate,pentaerythritol monopalmitate, pentaerythritol dipalmitate,pentaerythritol tripalmitate, pentaerythritol tetrapalmitate,pentaerythritol monostearate, pentaerythritol distearate,pentaerythritol tristearate, pentaerythritol tetrastearate,pentaerythritol monobehenate, pentaerythritol dibehenate,pentaerythritol tribehenate, pentaerythritol tetrabehenate,pentaerythritol monomontanate, pentaerythritol dimontanate,pentaerythritol trimontanate, pentaerythritol tetramontanate, sorbitanmonopalmitate, sorbitan dipalmitate, sorbitan tripalmitate, sorbitanmonostearate, sorbitan distearate, sorbitan tristearate, sorbitanmonobehenate, sorbitan dibehenate, sorbitan tribehenate, sorbitanmonomontanate, sorbitan dimontanate, sorbitan trimontanate, sorbitolmonopalmitate, sorbitol dipalmitate, sorbitol tripalmitate, sorbitolmonostearate, sorbitol distearate, sorbitol tristearate, sorbitolmonobehenate, sorbitol dibehenate, sorbitol tribehenate, sorbitolmonomontanate, sorbitol dimontanate, sorbitol trimontanate, and thelike. They may be used singly or as a mixture of two or more thereof.

In view of mechanical properties, releasing properties, slidingproperties, bleeding of the carboxylic acid onto the surface of moldedarticles, or contamination of organic substances attached to the mold,there may be mentioned, as preferred fatty acid esters, fatty acidesters of alcohols having 2 to 22, more preferably 2 to 20, mostpreferably 2 to 18 carbon atoms as monohydric or polyhydric alcoholswith saturated fatty acids or unsaturated fatty acids having 8 to 32,more preferably 10 to 24, most preferably 12 to 22 carbon atoms as fattyacids. Specifically, there may be mentioned stearyl stearate, behenylbehenate, ethylene glycol distearate, propylene glycol monostearate,propylene glycol monobehenate, glycerin monostearate, glycerinmonobehenate, sorbitan monostearate, sorbitan d-stearate, sorbitanmonobehenate, and the like.

The polyacetal resin composition of the invention is a polyacetal resincomposition comprising a polyacetal resin (I) and, per 100 parts byweight thereof, more than 5 parts by weight but less than 100 parts byweight of calcium carbonate (II) having an average particle diameter of0.1 to less than 1.5 μm and an average aspect ratio (L/D) of 3 or less,0.005 to 10 parts by weight of an organic acid (III), and 0 to less than0.05 part by weight of a fatty acid ester (IV), wherein the amount of Narelative to Ca is 250 ppm or less while the amount of Sr relative to Cais 500 to 2500 ppm. In view of obtaining a polyacetal resin compositionmore excellent in a balance of rigidity and toughness and excellent inanti-creep life and fatigue resistance, in the composition, the amountof Na relative to Ca is preferably 200 ppm or less, more preferably 150ppm or less, most preferably 100 ppm or less. Similarly, the amount ofSr relative to Ca is preferably from 600 to 1500 ppm, more preferablyfrom 700 to 1300 ppm, most preferably from 800 to 1000 ppm. At thistime, the amounts of Na and Sr relative to Ca in the composition can bedetermined by a high-frequency inductively-coupled plasma (IPC) emissionspectrometry. More specifically, 0.5 g of the polyacetal resincomposition is weighed in a platinum dish and carbonized in an electricfurnace at 500° C. After cooling, 5 mL of hydrochloric acid and 5 mL ofpure water are added thereto and the whole is boiled to dissolve on aheater. After cooling, pure water is added to adjust the concentrationto a measurable level and quantitative determination is carried out by ahigh-frequency inductively-coupled plasma (IPC) emission spectrometryusing IRIS/IP manufactured by Thermo Jarrell Ash based on acharacteristic wavelength of each metal. Thereafter, the amounts of Naand Sr relative to Ca are calculated.

Moreover, in the polyacetal resin composition of the invention, in viewof excellent thermal stability and moldability, formaldehyde-generatingrates, when the polyacetal resin (I) is heated at 220° C. under an argonstream, for heating periods of from 2 minutes to 10 minutes, from 10minutes to 30 minutes, and from 50 minutes to 90 minutes are eachpreferably 30 ppm/min. or less, more preferably 25 ppm/min. or less,most preferably 15 ppm/min. or less.

From the viewpoint that the polyacetal resin composition is moreexcellent in a balance of rigidity and toughness and excellent inanti-creep life and fatigue resistance, the amount of the calciumcarbonate (II) to be added is preferably more than 10 parts by weightbut less than 80 parts by weight, more preferably more than 15 parts byweight but less than 60 parts by weight, most preferably more than 20parts by weight but less than 50 parts by weight per 100 parts by weightof the polyacetal resin (I). For the same reason, the amount of theorganic acid (III) to be added is preferably from 0.01 to 8 parts byweight, more preferably from 0.015 to 5 parts by weight, most preferablyfrom 0.02 to 4 parts by weight per 100 parts by weight of the polyacetalresin (I). Moreover, in view of excellent balance of rigidity andtoughness, sliding properties and further stability of a plasticizationstep at molding, the amount of the fatty acid ester (IV) to be added ispreferably from 0 to 0.04 parts by weight, more preferably from 0 to0.03 parts by weight, most preferably from 0 to 0.02 parts by weight per100 parts by weight of the polyacetal resin (I).

In the invention, from the viewpoint that the resulting polyacetal resincomposition has more excellent balance of rigidity and toughness andfurther is excellent in anti-creep life and fatigue resistance, thecalcium carbonate (II) in the polyacetal resin composition is dispersedso that the maximum aggregated particle diameter is preferably 10 μm orless, more preferably 5 μm or less, most preferably 3 μm or less, stillmost preferably 1 μm or less. Furthermore, ideally, the calciumcarbonate is monodispersed in the state of an average particle diameterequal to the average particle diameter of the carbonate. The maximumaggregated particle diameter here means maximum size of the particlesformed by secondary aggregation of the calcium carbonate (II) in thepolyacetal resin composition. The maximum aggregated particle diameteris represented by a maximum value of the values obtained by forming aTYPE I test piece of ASTM D638 from pellets of the resin composition,cutting a thin piece out of a face perpendicular to the resin flowndirection at the central part of the test piece by means of a microtome,and observing the thin piece on a transmission electron microscope (TEM)(e.g., selected from the range of a photographic magnification of 10,000to 50,000 depending is on the degree of aggregation).

The process for producing the polyacetal resin composition of theinvention includes a method of dissolving the polyacetal resin (I) in asolvent, subsequently adding and mixing the calcium carbonate (II),organic acid (III), and fatty acid ester (IV), and removing the solvent,a method of adding and mixing the calcium carbonate (II), organic acid(III), and fatty acid ester (IV) to a heat-melt product of thepolyacetal resin (I), a method of adding the calcium carbonate (II),organic acid (III), and fatty acid ester (IV) formed beforehand as amasterbatch, or a method of combination thereof, and is not particularlylimited. Furthermore, the order of mixing the polyacetal resin (I),calcium carbonate (II), organic acid (III), and fatty acid ester (IV) isnot particularly limited and, for example, a method of mixing all orpart of the calcium carbonate (II), organic acid (III), and fatty acidester (IV) in a cone-type blender or the like and subsequently addingthe resulting mixture to a heat-melt product of the polyacetal resin (I)may be applied. Moreover, the calcium carbonate (II) and the organicacid (III) may be stirred and mixed using a Henschel mixer or the likeat a temperature equal to or higher than the melting point of theorganic acid (III), and the surface of the calcium carbonate (II) may becoated therewith.

Among them, in view of excellent productivity, as a preferred productionmethod, there may be mentioned a method of adding and mixing the calciumcarbonate (II), organic acid (III), and fatty acid ester (IV) to aheat-melt product of the polyacetal resin (I), i.e., a melt-kneadingmethod.

In the case of production by the above melt-kneading method, as anapparatus therefor, a kneader commonly practically used can be applied.For example, a single-screw or multi-screw kneading extruder, a roll, ora Bumbury mixer, or the like may be employed. Of these, a twin-screwextruder equipped with a pressure-reducing apparatus and a side-feederequipment is most preferred. As the melt-kneading method, there may bementioned a method of kneading all the components simultaneously, akneading method using a blend pre-kneaded beforehand, a method offeeding individual components sequentially at the midstream of theextruder and kneading them, or the like method. Moreover, it is possibleto disperse the calcium carbonate (II) and the like in a solventbeforehand, which can be added in the slurry state. In that case, it canbe also fed using a liquid-feeding pumps

The conditions for the melt kneading are not particularly limited butthe degree of reduced pressure is preferably from 0 to 0.07 MPa. Thetemperature for kneading is preferably a temperature that is higher, byfrom 1 to 100° C., than the melting point or softening point determinedby differential scanning calorimetry (DSC) in accordance with JIS K7121.More specifically, the temperature is from 160° C. to 240° C. The shearrate in the kneader is preferably 100 (SEC⁻¹) or more and the averageresidence time at kneading is preferably from 1 to 15 minutes. Thesolvent in the resin composition is preferably 1% by weight or less.When the conditions fall within the above ranges, productivity isexcellent and color change of the resulting polyacetal resin compositiontends to be suppressed.

In the above melt-kneading method, in view of obtaining more excellentin a balance of mechanical properties, such as rigidity and toughness,and particularly excellent in anti-creep life, as an even more preferredproduction method, there may be mentioned a process for producing apolyacetal resin composition comprising a step of simultaneouslymelt-kneading a polyacetal resin (I) and, per 100 parts by weightthereof, more than 5 parts by weight but less than 100 parts by weightof calcium carbonate (II) which has an average particle diameter of from0.1 μm to less than 1.5 μm and an average aspect ratio (L/D) which is aratio of average major axis (L) of particles to average minor axis (D)of particles of 3 or less and which is not surface-treated with asaturated fatty acid, unsaturated fatty acid and metal salt thereofhaving 8 to 32 carbon atoms, and 0.005 to 10 parts by weight of anorganic acid (III), at melting point of the polyacetal resin (I) orhigher. More specifically, the process comprises simultaneous kneadingof both of the calcium carbonate (II) and the organic acid (III) such asa saturated or unsaturated fatty acid having 8 to 32 carbon atoms in amelted state of the polyacetal resin (I) without a step ofsurface-treating or coating the calcium carbonate (II) beforehand with asaturated or unsaturated fatty acid having 8 to 32 carbon atoms or ametal salt of the saturated or unsaturated fatty acid having 8 to 32carbon atoms which corresponds to the organic acid (III) by Henschelcoating or the like. In the production process, the reason whyanti-creep life or the like is particularly excellent is not clear butis presumed that the polyacetal resin (I), the calcium carbonate (II),and the organic acid (III) form a good interface simultaneously to theirdispersion.

The polyacetal resin composition of the invention has characteristics ofexcellent balance of thermal stability and mechanical properties, suchas rigidity and toughness, and also excellent anti-creep life, fatigueresistance and acid resistance, but a polyacetal resin compositionfurther comprising a polyalkylene glycol (v) added thereto in an amountof 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, morepreferably 0.5 to 3 parts by weight, most preferably 1.0 to 2.0 parts byweight, per 100 parts by weight of the polyacetal resin composition ismore excellent in acid resistance, particularly durability againstsulfur oxides with maintaining the balance of mechanical properties suchas rigidity and toughness, anti-creep life, and the like. Therefore, itcan be expected to use it for parts which come into direct contact withgasoline fuel or diesel fuel, e.g., pump modules which are large-sizedparts, and fuel valves, fuel tank flanges, fuel level gauges, and thelike.

The above polyalkylene glycol (V) is a polycondensate obtained from analkylene glycol as a monomer and is not particularly limited so long asit is known. For example, there may be mentioned polyethylene glycol,polypropylene glycol, polyethylene glycol-polypropylene glycol blockcopolymers, and the like.

With regard to the alkylene glycol, part or all of the terminals may beetherified with an aliphatic alcohol. For example, there may bementioned polyethylene glycol oleyl ether, polyethylene glycol cetylether, polyethylene glycol stearyl ether, polyethylene glycol laurylether, polyethylene glycol tridecyl ether, polyethylene glycolnonylphenyl ether, polyethylene glycol octylphenyl ether, and the like.

In addition, with regard to the alkylene glycol, part or all of theterminals may be esterified with a fatty acid. Specifically, there maybe mentioned polyethylene glycol monolaurate, polyethylene glycolmonostearate, polyethylene glycol monooleate, and the like.

Of these, in view of cost, as a preferred polyalkylene glycol (V), theremay be mentioned polyethylene glycol or polypropylene glycol.Furthermore, in view of excellent durability against an acid, thenumber-average molecular weight is preferably from 10,000 to 45,000,more preferably from 13,000 to 35,000, even more preferably from 15,000to 25,000.

The method of adding and mixing the polyalkylene glycol (V) is notparticularly limited and, for example, it may be added at the productionof the polyacetal resin composition comprising the above (I) to (IV) ormay be added to the polyacetal resin composition by the melt-kneadingmethod or the masterbatch method.

In the invention, appropriate known additives can be further blended, ifnecessary, within the range where the purpose of the invention is notimpaired. Specifically, there may be mentioned an antioxidant, a heatstabilizer, a weather-resistant (light) stabilizer, a mold-releasingagent, a slidability-imparting agent, a lubricant, a crystal nucleatingagent, an inorganic filler, a conductive material, a thermoplastic resinand thermoplastic elastomer, a pigment, and the like.

The present polyacetal resin composition of the invention is excellentin a balance of thermal stability and mechanical properties, such asrigidity and toughness, also excellent in anti-creep life, fatigueresistance and acid resistance. In addition, it is excellent in warp ofmolded articles and weld strength, it can be used in parts of variousapplications. For example, it can be suitably used as mechanism partssuch as gears, cams, sliders, levers, arms, clutches, felt clutches,idler gears, pulleys, rollers, logs, key stems, key tops, shutters,reels, shafts, hinges, shafts, bearings, and guides; resin carts ofinsert molding, chassis, trays, side plates, parts for office automationequipment such as printers and copiers, parts for camera or videoequipment such as VTR (Video Tape Recorder), video movie, digital videocamera, camera, and digital camera; music, picture or informationequipment such as cassette players, DAT, LD (Laser Disk), MD (MiniDisk), CD (Compact Disk) [including CD-ROM (Read Only Memory), CD-R(Recordable) and CD-RW (Rewritable)], DVD (Digital Video Disk)[including DVD-ROM, DVD-R, DVD-RW, DVD-RAM (Random Access Memory) andDVD Audio]; other optical disk drives, MFD, MO, navigation system, andmobile personal computer; communication equipment such as portabletelephone and facsimile; parts for electric devices, parts forelectronic devices, automobile parts such as fuel-related parts, e.g.gasoline fuel or diesel fuel tanks, fuel pump modules, valves, gasolinetank flanges, etc.; door-related parts, e.g. door locks, door handles,window regulators, speaker grills, etc.; seat belt-related parts, e.g.seat belt slip rings, press buttons, etc.; combination switch parts,switches and parts of clips; pen tips of mechanical pencils andmechanism parts for taking in or out of lead of mechanical pencils;wash-basin and drains, and mechanism parts for opening and closing wasteplug, rocking mechanism for drawspan of vending machines and parts forgoods-discharging mechanism; code stoppers, adjusters, and bottoms forcloths; water spray nozzles and connecting joints for water-spray hoses;building articles such as handrails for stairs, supports for floorings,and structural parts for electric shutters; disposable cameras; toys;playing machine-related ones such as pachinko and pinball machines;fasteners; chains; conveyors; buckles; rollers; reduction equipment;joints; sport article parts; vending machines; furniture; musicalinstruments; and industrial parts such as furniture-housingfacility-related devices.

EXAMPLES

The following will describe the invention further in detail withreference to Examples, but the invention is not limited to the followingexamples. In this connection, evaluation described in the followingExamples and Comparative Examples was carried out by the followingmethods.

(1) Melt Flow Index (MFI: g/10 min.)

Measured under conditions of 190° C. and 2,160 g using MELT INDEXER,manufactured by Toyo Seiki K.K. according to ASTM-D1238.

(2) Measurement of Formaldehyde-Generating Rate (ppm/min.) of PolyacetalResin and Polyacetal Resin Composition

Under a nitrogen stream (50 NL/hr), 3 g of pellets of the polyacetalresin or polyacetal resin composition subjected to drying treatment at140° C. for 1 hour beforehand was heated to melt at 220° C. andformaldehyde generated has absorbed in water and then titrated by asodium sulfite method. At that time, when the amount (ppm) offormaldehyde generated from the start of heating until 2 minutes laterwas taken as Y₂, the amount until 10 minutes later as Y₁₀, the amountuntil 30 minutes later as Y₃₀, the amount until 50 minutes later as Y₅₀,and the amount until 90 minutes later as Y₉₀, theformaldehyde-generating rates were calculated as follows:

Generating rate from 2 minutes to 10 minutes: (Y₁₀−Y₂)/8 (ppm/min.),

Generating rate from 10 minutes to 30 minutes: (Y₃₀−Y₁₀)/20 (ppm/min.),and

Generating rate from 50 minutes to 90 minutes: (Y₉₀−Y₅₀)/40 (ppm/min.).These values are derived from the formaldehyde attached to thepolyacetal resin, derived from the formaldehyde generated bydecomposition of terminals of the polyacetal resin, and derived from theformaldehyde generated by decomposition of main chain of the polyacetalresin, respectively. The smaller these values are, the more excellentthe thermal stability is.

(3) Observation on Scanning Electron Microscope (SEM)

The average particle diameter, average aspect ratio (measurement ofaverage major axis and average minor axis), and shape of particles ofcalcium carbonate and coupling agent-treated calcium carbonate wereobserved and determined using the following apparatus:

Fine coater: JFC-1600 manufactured by JOEL Ltd. Coating was conductedunder conditions of 30 mA and 60 seconds;

Scanning electron microscope: JSM-6700F manufactured by JOEL Ltd.

Measurement was conducted under conditions of a acceleration voltage of9.00 kV and an applied current of 10.0 μA.

The average particle diameter was determined by measuring each length ofat least 100 particles randomly selected from the obtained particleimage, followed by calculation according to the expression:Average particle diameter=average major axis=ΣL _(i) ² N _(i) /ΣL _(i) N_(i).

The average aspect ratio was determined by measuring each major axis andminor axis of at least 100 particles randomly selected from the obtainedparticle image, followed by calculation according to the expressions:Average major axis=ΣL _(i) ² N _(i) /ΣL _(i) N _(i)Average minor axis=Σd _(i) ² N _(i) /Σd _(i) N _(i)Average aspect ratio L/d=(ΣL _(i) ² N _(i) /ΣL ₁ N _(i))/(Σd _(i) ² N ₁/Σd _(i) N _(i)).(4) Quantitative Determination of Ca, Na, and Sr in Calcium Carbonateand Polyacetal Resin Composition and Calculation of Amounts of Na and SrRelative to Ca

0.5 g of calcium carbonate or a polyacetal resin composition was weighedin a platinum dish and carbonized in an electric furnace at 500° C.After cooling, 5 mL of hydrochloric acid and 5 mL of pure water wereadded thereto and the whole was boiled to dissolve on a heater. Aftercooling, pure water was added to adjust the concentration to ameasurable level and quantitative determination was carried out by ahigh-frequency inductively-coupled plasma (IPC) emission spectrometryusing IRIS/IP manufactured by Thermo Jarrell Ash based on acharacteristic wavelength of each metal. Thereafter, the amounts of Naand Sr relative to Ca were calculated.

(5) Observation on Transmission Electron Microscope (TEM) Observation ofMaximum Aggregated Particle Diameter

A TYPE I test piece of ASTM D638 was formed under injection moldingconditions of an injection of 15 seconds and cooling of 25 seconds usingan injection molding machine (SH-75 manufactured by Sumitomo HeavyIndustries, Ltd.) with setting a cylinder temperature of 200° C. and amold temperature of 70° C., and an ultra-thin piece of about 50 nm wascut out of a face perpendicular to the resin flown direction at thecentral part of the test piece by means of a cryomicrotome manufacturedby ReichertNissei. In the observation on a transmission electronmicroscope (TEM), a bright-field image having a magnitude of 5,000 to30,000 was photographed using HF 2000 manufactured by HitachiCorporation and maximum size of each secondary aggregated particles wasmeasured, a maximum value of the values being regarded as the maximumaggregated particle diameter. However, when the size of each particleformed is obviously larger than the average particle diameter of calciumcarbonate added, it is judged to be other additive and thus was excludedfrom the measurement.

(6) Physical Properties of Polyacetal Resin Composition

A dumbbell piece or strip piece for evaluation was obtained underinjection molding conditions of an injection of 15 seconds and coolingof 25 seconds using an injection molding machine (SH-75 manufactured bySumitomo Heavy Industries, Ltd.) with setting cylinder temperature at200° C. and mold temperature at 70° C. Evaluation was conductedaccording to the following items.

(6-1) Stability of Plasticizing Step at Molding

The stability of the plasticizing step was evaluated on the followingitems.

A plasticizing time was stable.

B plasticizing time slightly varied.

C plasticizing time varied and a problem of idling of screw arose.

(6-2) Flexural Elastic Modulus (GPa) and Flexural Strength (MPa)

Measured in accordance with ASTM D790.

(6-3) Tensile Elongation (%) and Tensile Strength (MPa)

Measured in accordance with ASTM D638.

(6-4) Izod Impact Strength with Notch

Measured in accordance with ASTM D256.

(6-5) Acid Resistance Test

A JIS No. 3 type dumbbell piece for evaluation was obtained underinjection molding conditions of an injection of 15 seconds and coolingof 25 seconds using an injection molding machine (SH-75 manufactured bySumitomo Heavy Industries, Ltd.) with setting cylinder temperature at200° C. and mold temperature at 70° C. The dumbbell piece was placed ina glass pressure bottle, a mixed aqueous solution prepared by mixingequal volumes of 0.1N aqueous formic acid solution and 0.1N aqueoussulfuric acid solution was added thereto, and the bottle was tightlysealed, followed by heat treatment at 130±5° C. for 3 and 6 hours. Then,the dumbbell piece was washed with tap water and dried at 23° C. under ahumidity of 50% for 48 hours. At that time, the weight loss, retentionof tensile strength (the following expression), and tensile elongationafter the test were determined. Weight loss=(Weight of dumbbell pieceafter test)/(Weight of dumbbell piece before test)×100 (%) Retention oftensile strength=(Tensile strength after test)/(Tensile strength beforetest)×100 (%)

(6-6) Sliding Test

Using a pin/plate tester AFT-15MS manufactured by Toyo Precision PartsMfg. Co. Ltd., SUS 314 was set at the pin side and the dumbbell piecefor evaluation at the plate side. Test was conducted under conditions ofa reciprocating time of 30 mm/s and a reciprocating distance of 20 mm, aload of 2 kg, a temperature of 25° C., and a humidity of 50%. At thattime, friction coefficient at reciprocation of 5000 times was measuredand the scraped amount of the dumbbell piece after completion of thetest was measured as abrasion depth (μm).

(6-7) Creep Test

Using a creep tester 100-6 manufactured by Toyo Seimitsu SeisakusyoK.K., the JIS No. 3 type dumbbell test piece was tested under conditionsof a load stress of 10 MPa and a temperature of 130° C. and timerequired until the tensile test piece is broken was compared. Moreover,the following components were used in Examples and Comparative Examples.

<Polyacetal Resins>

(a-1) Polyacetal resin (copolymer) of Asahi Kasei Chemicals Corporation,Tenac (registered trademark) HC450

MFI=10 g/10 min.

Formaldehyde-generating rate:(Y ₁₀ −Y ₂)/8 (ppm/min.)=6(Y ₃₀ −Y ₁₀)/20 (ppm/min.)=8(Y ₉₀ −Y ₅₀)/40 (ppm/min.)=7(a-2) Mixture of 65 parts by weight of polyacetal resin (copolymer) ofAsahi Kasei Chemicals Corporation, Tenac (registered trademark) HC450and 35 parts by weight of polyacetal resin (copolymer) of Asahi KaseiChemicals Corporation, Tenac (registered trademark) HC750

MFI=15 g/10 min.

Formaldehyde-generating rate:(Y ₁₀ −Y ₂)/8 (ppm/min.)=7(Y ₃₀ −Y ₁₀)/20 (ppm/min.)=10(Y ₉₀ −Y ₅₀)/40 (ppm/min.)=7(a-3) Polyacetal resin (copolymer) of Asahi Kasei Chemicals Corporation,Tenac (registered trademark) 4520

MFI=10 g/10 min.

Formaldehyde-generating rate:(Y ₁₀ −Y ₂)/8 (ppm/min.)=3(Y ₃₀ −Y ₁₀)/20 (ppm/min.)=4(Y ₉₀ −Y ₅₀)/40 (ppm/min.)=3(a-4) Polyacetal resin (block copolymer) of Asahi Kasei ChemicalsCorporation, Tenac (registered trademark) AC450

MFI=10 g/10 min.

Formaldehyde-generating rate:(Y ₁₀ −Y ₂)/8 (ppm/min.)=4(Y ₃₀ −Y ₁₀)/20 (ppm/min.)=3(Y ₉₀ −Y ₅₀)/40 (ppm/min.)=8(a-5) Polyacetal resin (homopolymer) of Asahi Kasei ChemicalsCorporation, Tenac (registered trademark) 4010

MFI=10 g/10 min.

Formaldehyde-generating rate:(Y ₁₀ −Y ₂)/8 (ppm/min.)=2(Y ₃₀ −Y ₁₀)/20 (ppm/min.)=3(Y ₉₀ −Y ₅₀)/40 (ppm/min.)=2<Calcium Carbonate>(b-1) Kalfain 200M manufactured by Maruo Calcium Co. Ltd.(b-2) Calcium carbonate manufactured by Konoshima Chemical Co., Ltd.(b-3) A product obtained by adding 3 parts by weight of stearic acid(F-3 manufactured by Kawaken Fine Chemicals Co., Ltd.) to 100 parts byweight of calcium carbonate manufactured by Konoshima Chemical Co., Ltd.and stirring them in Henschel mixer at 120° C. at 5000 rpm for 10minutes, followed by surface treatment(b-4) MSK-PO manufactured by Maruo Calcium Co. Ltd.(b-5) Brilliant-15 manufactured by Shiraishi Kogyo Kaisha Ltd.(b-6) A product obtained by similarly subjecting Brilliant-15manufactured by Shiraishi Kogyo Kaisha Ltd.(b-5) to surface treatment with stearic acid(b-7) Kaltex 5 manufactured by Maruo Calcium Co. Ltd.(b-8) A product obtained by subjecting Kaltex 5 manufactured by MaruoCalcium Co, Ltd. (b-7) to surface treatment with stearic acid similarlyto (b-6)(b-9) Nanocoat S-25 manufactured by Maruo Calcium Co. Ltd.(b-10) PC manufactured by Shiraishi Kogyo Kaisha Ltd.(b-11) A product obtained by subjecting PC manufactured by ShiraishiKogyo Kaisha Ltd. (b-10) to surface treatment with stearic acidsimilarly to (b-6)(b-12) Silver W manufactured by Shiraishi Kogyo Kaisha Ltd.(b-13) A product obtained by subjecting Silver W manufactured byShiraishi Kogyo Kaisha Ltd. (b-12) to surface treatment with stearicacid similarly to (b-6)(b-14) Super S manufactured by Maruo Calcium Co. Ltd.(b-15) A product obtained by subjecting Super S manufactured by MaruoCalcium Co. Ltd. (b-14) to surface treatment with stearic acid similarlyto (b-6)(b-16) R heavy carbonate manufactured by Maruo Calcium Co. Ltd.(b-17) A product obtained by subjecting R heavy carbonate manufacturedby Maruo Calcium Co. Ltd. (b-16) to surface treatment with stearic acidsimilarly to (b-6)<Organic acid>(c-1) Stearic acid (F-3 manufactured by Kawaken Fine Chemicals Co.,Ltd.)<Fatty Acid Ester>(d-1) Ethylene glycol distearate (Unistar E275 manufactured by NOFCorporation)<<Polyalkylene Glycols>(e-1) Ethylene glycol (PEG-20000 manufactured by Sanyo ChemicalIndustries, Ltd.)(e-2) Ethylene glycol (PEG-6000P manufactured by Sanyo ChemicalIndustries, Ltd.)<<Other Additive>(f-1) Hydrotalcite Mg_(4.3)Al₂(OH)₁₂.6CO₃ (DHT-4C manufactured by KyowaChemical Industry Co., Ltd.)[Various Physical Properties of Calcium Carbonate]

Table 1 shows kind, average particle diameter, average aspect ratio, andthe like of calcium carbonates used.

Examples 1 to 30 and Comparative Examples 1 to 22

Polyacetal resin, calcium carbonate, organic acid, and the like wereweighed in blending amounts shown in Tables 2 to 6. Using a twin-screwextruder (PCM-30 manufactured by Ikegai Ltd.), each of them was addedfrom the top of the extruder and the whole was melt-kneaded to obtain apolyacetal resin composition. At that time, the melt-kneading wasconducted under conditions of a temperature of 200° C. and a rotationnumber of 150 rpm. The evaluation results are shown in Tables 2 to 6.

TABLE 1 Calcium carbonate b-1 b-2 b-3 b-4 b-5 b-6 b-7 b-8 b-9 b-10 Kindlight light light light light light heavy heavy heavy light Average 0.050.08 0.08 0.15 0.20 0.20 0.6 0.6 1.0 1.2 particle diameter (μm) Average1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 2.5 aspect ratio (L/d) BET 16 18 1710 12 12 9 9 9 5 adsorbed amount Amount of 700 750 750 560 50 50 30 3015 30 Na relative to Ca (ppm) Amount of 260 700 700 220 820 820 330 330330 790 Sr relative to Ca (ppm) Surface yes no yes yes no yes no yes yesno treatment acid Calcium carbonate b-11 b-12 b-13 b-14 b-15 b-16 b-17Kind light light light heavy heavy heavy heavy Average 1.2 2.0 2.0 4.04.0 40 40 particle diameter (μm) Average 2.5 3.8 3.8 1.0 1.0 1.0 1.0aspect ratio (L/d) BET 5 6 6 5 5 3 3 adsorbed amount Amount of 30 30 3020 20 20 20 Na relative to Ca (ppm) Amount of 790 1030 1030 400 400 380380 Sr relative to Ca (ppm) Surface yes no yes no yes no yes treatmentacid

TABLE 2 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10Com. Ex. 1 Com. Ex. 2 Polyacetal resin Kind a-1 a-1 a-1 a-1 a-1 a-1 a-1a-1 a-1 a-1 a-1 a-1 Amount added 100 100 100 100 100 100 100 100 100 100100 100 Calcium carbonate Kind b-5 b-5 b-5 b-5 b-6 b-6 b-10 b-10 b-11b-11 — b-5 Crystal light light light light light light light light lightlight — light Average particle 0.20 0.20 0.20 0.20 0.20 0.20 1.2 1.2 1.21.2 — 0.20 diameter (μm) Average aspect 1.0 1.0 1.0 1.0 1.0 1.0 2.5 2.52.5 2.5 — 1.0 ratio (L/d) Surface treatment no no no no yes yes no noyes yes — no with fatty acid Amount added 10 20 30 40 20.6 41.2 20 4020.6 41.2 — 20 Organic acid Kind c-1 c-1 c-1 c-1 (c-1) (c-1) c-1 c-1(c-1) (C-1) — — Amount added 0.3 0.60 0.90 1.20 (0.60)* (1.20)* 0.601.20 (0.60)* (1.20)* — — Physical properties of resin composition Amountof Na to Ca 50 50 50 50 50 50 30 30 30 30 less than 1 less than 1 Amountof Sr to Ca 820 820 820 820 820 820 790 790 790 790 less than 1 lessthan 1 Formaldehyde- generating rate (ppm/min) 2 to 10 min 12 18 22 2616 25 21 30 24 26 7 50 10 to 30 min 10 14 15 24 14 22 12 21 11 22 8 6650 to 90 min 10 16 17 28 15 25 12 23 11 22 7 100 or more Flexuralelastic 3.02 3.28 3.50 3.85 3.18 3.79 3.26 3.88 3.18 3.80 2.75 coloredmodulus (GPa) brown and Flexural strength 92 89 85 81 87 80 88 82 87 8292 foamed (MPa) through Tensile elongation 40 45 51 38 45 32 43 43 43 2442 melt- (%) kneading, Tensile strength 55 50 44 40 50 42 51 43 50 42 62thus (MPa) difficult Izod with notch 72 71 67 65 66 61 63 46 63 48 60 tomold (J/m) Creep test 10 MPa, 130° C. Break time (min) — 1420 — — 630 —1450 — 960 — 1300 Acid-resistant test Weight loss after — 7.5 — — 7.1 —8.4 — 7.6 — 16.5 3 h (wt %) Weight loss after — 10.2 — — 10.3 — 10.5 —11.0 — 35.2 6 h (wt %) *The amount of surface treatment to calciumcarbonate is described.

TABLE 3 C. Ex. C. Ex. C. Ex. C. Ex. C. Ex. C. Ex. C. Ex. C. Ex. C. Ex.C. Ex. C. Ex. C. Ex. C. Ex. 3 4 5 6 7 8 9 10 11 12 13 14 15 Polyacetalresin Kind a-1 a-1 a-1 a-1 a-1 a-1 a-1 a-1 a-1 a-1 a-1 a-1 a-1 Amountadded 100 100 100 100 100 100 100 100 100 100 100 100 100 Calciumcarbonate Kind b-1 b-2 b-3 b-4 b-7 b-8 b-12 b-13 b-14 b-15 b-16 b-16b-17 Crystal light light light light heavy heavy heavy light light heavyheavy heavy heavy Average particle 0.05 0.08 0.08 0.15 0.6 0.6 1.0 2.02.0 4.0 4.0 40 40 diameter (μm) Average aspect 1.0 1.0 1.0 1.0 1.0 1.01.0 3.8 3.8 1.0 1.0 1.0 1.0 ratio (L/d) Surface treatment yes no yes yesno yes yes no yes no yes no yes with fatty acid Amount added 20.6 2020.6 20.6 20 20.6 20.6 20 20.6 20 20.6 20 20.6 Organic acid treatedtreated treated Kind Amount added c-1 (c-1) c-1 (c-1) c-1 (c-1) c-1(c-1) c-1 (c-1) Physical properties 0.60 (0.60)* 0.60 (0.60)* 0.60(0.60)* 0.60 (0.60)* 0.60 (0.60)* of resin composition Amount of Na toCa 700 750 750 560 30 30 15 30 30 20 20 20 20 (ppm) Amount of Sr to Ca260 700 700 220 330 330 330 1030 1030 400 400 380 380 (ppm)Formaldehyde- generating rate (ppm/min) 2 to 10 min 55 48 49 25 21 20 2125 25 28 30 35 35 10 to 30 min 42 33 35 21 20 22 22 19 20 25 24 29 30 50to 90 min 32 28 27 22 19 21 19 18 18 20 19 28 27 Flexural elastic 3.283.35 3.32 3.25 3.20 3.20 3.20 3.29 3.24 3.01 2.94 2.93 2.81 modulus(GPa) Flexural strength 90 91 90 90 88 89 89 89 89 85 84 84 83 (MPa)Tensile elongation 33 27 27 35 44 42 44 45 50 25 19 17 10 (%) Tensilestrength 50 51 51 51 50 50 51 52 52 49 49 49 49 (MPa) Izod with notch 4144 44 59 63 60 51 45 45 35 36 34 34 (J/m) Creep test 10 MPa, 130° C.Break time (min) 890 770 740 600 450 450 340 1190 1270 250 250 160 150Acid-resistant test Weight loss after 6.7 6.9 6.9 6.9 8.5 7.7 7.8 8.57.6 8.9 7.9 8.8 7.6 3 h (wt %) Weight loss after 10.1 10.2 10.1 10.110.3 10.4 11.2 10.7 11.0 11.7 12.1 11.8 11 6 h (wt %) *The amount ofsurface treatment to calcium carbonate is described.

TABLE 4 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16 Ex. 17 Ex. 18 Ex. 19C. Ex. 16 C. Ex. 17 C. Ex 18 Polyacetal resin Kind a-3 a-3 a-3 a-4 a-4a-4 a-5 a-5 a-5 a-3 a-4 a-5 Amount added 100 100 100 100 100 100 100 100100 100 100 100 Calcium carbonate Kind b-5 b-5 b-5 b-5 b-5 b-5 b-5 b-5b-5 — — — Crystal light light light light light light light light light— — — Average particle 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 — —— diameter (μm) Average aspect 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 — — —ratio (L/d) Surface treatment no no no no no no no no no — — — withfatty acid Amount added 10 20 30 10 20 30 10 20 30 — — — Organic acidKind c-1 c-1 c-1 c-1 c-1 c-1 c-1 c-1 c-1 — Amount added 0.30 0.60 0.900.30 0.60 0.90 0.30 0.60 0.90 — Physical properties of resin composltionAmount of Na to Ca 50 50 50 50 50 50 50 50 50 less than 1 less than 1less than 1 (ppm) Amount of Sr to Ca 820 820 820 820 820 820 820 820 820less than 1 less than 1 less than 1 (ppm) Flexural elastic 2.72 2.953.23 2.32 2.43 2.56 3.42 3.77 4.15 2.49 2.41 3.07 modulus (GPa) Flexuralstrength 85 82 78 78 75 72 100 100 96 85 86 100 (MPa) Tensile elongation40 43 45 40 61 50 27 27 26 42 37 35 (%) Tensile Strength 49 44 39 47 4239 60 54 50 58 55 68 (MPA) Izod with notch 65 68 63 87 79 73 62 58 58 6061 68 (J/m) Creep test 10 MPa, 130° C. Break time (min) — 980 — — 330 —— 2130 — 770 300 1800

TABLE 5 Example Example Example Example Example Com. Example 20 21 22 2324 19 Polyacetal resin Kind a-2 a-2 a-2 a-2 a-2 a-2 Amount added 100 100100 100 100 100 Calcium carbonate Kind b-5 b-5 b-5 b-5 b-5 — Crystallight light light light light — Average particle 0.20 0.20 0.20 0.200.20 — diameter (μm) Average aspect ratio 1.0 1.0 1.0 1.0 1.0 — (L/d)Amount added 20 20 20 20 20 — Organic acid Kind c-1 c-1 c-1 c-1 c-1 —Amount added 0.60 0.60 0.60 0.60 0.60 — Fatty acid ester Kind — d-1 d-1d-1 d-1 — Amount added — 0.06 0.20 1.0 4.0 — Stability of plastic- A A BC C A izaton step at molding Physical properties of resin compositionAmount of Na to Ca 50 50 50 50 50 less than 1 (ppm) Amout of Sr to Ca820 820 820 820 820 less than 1 (ppm) Flexural elastic 3.38 3.37 3.343.3 2.94 2.72 modulaus (GPa) Flexural strength 88 89 88 87 83 91 (MPa)Tensile elongation (%) 51 39 41 26 29 45 Tensile strength (MPa) 49 48 4948 47 61 Izod with notch (J/m) 68 65 65 58 50 60 Sliding propertiesFriction coefficient 0.17 0.11 0.12 0.14 0.14 0.14 at firstreciprocation Friction coefficient 0.21 0.39 0.33 0.32 0.15 0.33 at5000th reciprocation Increase in friction 0.04 0.28 0.21 0.18 0.01 0.19coefficient Abrasion of test piece 10 34 24 22 6 7 after 5000 times ofreciprocation (μm)

TABLE 6 Ex. 25 Ex. 26 Ex. 27 Ex. 28 Ex. 29 Ex. 30 C. Ex. 19 C. Ex. 20 C.Ex. 21 C. Ex. 22 Polyacetal resin Kind a-2 a-2 a-2 a-2 a-2 a-2 a-2 a-2a-2 a-2 Amount added 100 100 100 100 100 100 100 100 100 100 Calciumcarbonate Kind b-5 b-5 b-5 b-5 b-5 b-5 — — — — Crystal light light lightlight light light — — — — Average particle 0.20 0.20 0.20 0.20 0.20 0.20— — — — diameter (μm) Average aspect 1.0 1.0 1.0 1.0 1.0 1.0 — — — —ratio (L/d) Amount added 10 10 10 10 20 30 — — — — Organic acid Kind c-1c-1 c-1 c-1 c-1 c-1 — — — — Amount added 0.3 0.3 0.3 0.3 0.6 0.9 — — — —Polyalkylene glycol Kind e-1 e-1 e-1 e-1 e-1 e-1 — e-1 — e-1 Amountadded 1.0 2.0 1.0 2.0 1.0 0.5 — 1.0 — 1.0 Other additive Kind f-1 f-1f-1 f-1 f-1 f-1 f-1 f-1 Amount added 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5Physical properties of resin composition Amount of Na to Ca 50 50 50 5050 50 less than 1 less than 1 less than 1 less than 1 (ppm) Amount of Srto Ca 820 820 820 820 820 820 less than 1 less than 1 less than 1 lessthan 1 (ppm) Flexural elastic 2.93 2.73 3.02 2.77 3.00 3.35 2.72 2.762.76 2.73 modulus (GPa) Flexural strength 87 82 89 84 80 82 91 89 90 86(MPa) Tensile elongation 27 35 30 26 71 44 45 33 30 35 (%) Tensilestrength 55 53 57 55 47 43 61 59 61 59 (MPa) Izod with notch 62 65 60 6075 69 60 52 57 52 (J/m) Acid resistance Weight loss after 6.7 6.0 9.610.3 4.7 4.1 14.9 6.8 8.5 7.2 3 h wt % Tensile strength 99 100 95 95 10098 92 93 94 92 retention after 3 h % Tensile elongation 23 27 20 21 5661 12 23 16 20 after 3 h % Weight loss after 10.8 9.8 14.3 15.1 6.3 5.231.6 19.3 24.2 20.2 6 h wt % Tensile strength 97 96 96 95 99 97 64 89 9185 retention after 6 h % Tensile elongation 14 12 15 15 18 14 7 19 11 15after 6 h %

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

The present application is based on Japanese Patent Application No.2004-012980 filed on Jan. 21, 2004, Japanese Patent Application No.2004-091048 filed on Mar. 26, 2004, and Japanese Patent Application No.2004-091049 filed on Mar. 26, 2004, and the contents are incorporatedherein by reference.

INDUSTRIAL APPLICABILITY

The resin composition of the invention is excellent in a balance ofthermal stability and mechanical properties, such as rigidity andtoughness, also excellent in anti-creep life, fatigue resistance andacid resistance, so that it can be suitably used in various fields, suchas automobile, electrical/electronic and other industries.

1. A polyacetal resin composition comprising: (I) a polyacetal resin;and per 100 parts by weight thereof, (II) more than 5 parts by weightbut less than 100 parts by weight of calcium carbonate, wherein thecalcium carbonate has an average particle diameter of from 0.1 μm toless than 1.5 μm and an average aspect ratio (L/D) which is a ratio ofaverage major axis (L) of particles to average minor axis (D) ofparticles of 3 or less; (III) 0.005 to 10 parts by weight of an organicacid; and (IV) 0 to less than 0.05 parts by weight of a fatty acidester, wherein the amount of Na relative to Ca is 250 ppm or less andthe amount of Sr relative to Ca is from 500 to 2500 ppm.
 2. Thepolyacetal resin composition according to claim 1, wherein the amount ofNa relative to Ca in the composition is 100 ppm or less.
 3. Thepolyacetal resin composition according to claim 1, wherein the amount ofSr relative to Ca in the composition is from 600 to 1500 ppm.
 4. Thepolyacetal resin composition according to claim 1, whereinformaldehyde-generating rates, at the time when the polyacetal resin (I)is heated at 220° C. under an argon stream, for heating periods of from2 minutes to 10 minutes, from 10 minutes to 30 minutes and from 50minutes to 90 minutes are each 15 ppm/min or less.
 5. The polyacetalresin composition according to claim 4, wherein the polyacetal resin (I)is a heat-stabilized polyacetal resin obtained by treating to stabilizethermally unstable terminals with at least one quaternary ammoniumcompound represented by the following formula:[R¹R²R³R⁴N⁺]_(n)X^(−n) wherein R¹, R², R³, R⁴ each independentlyrepresents an unsubstituted or substituted alkyl group having 1 to 30carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkylgroup in which an unsubstituted or substituted alkyl group having 1 to30 carbon atoms is substituted with at least one aryl group having 6 to20 carbon atoms, or an alkylaryl group in which an aryl group having 6to 20 carbon atoms is substituted with at least one unsubstituted orsubstituted alkyl group having 1 to 30 carbon atoms, provided that theunsubstituted or substituted alkyl group may be any of linear, branchedor cyclic, and that in the unsubstituted alkyl group, aryl group,aralkyl group or alkylaryl group, hydrogen atom(s) may be substitutedwith halogen(s); n represents an integer of 1 to 3; and X represents ahydrogen atom, or an acid residue of a carboxylic acid having 1 to 20carbon atoms, a hydroacid, an oxo acid, an inorganic thio acid or anorganic thio acid having 1 to 20 carbon atoms.
 6. The polyacetal resincomposition according to claim 5, wherein the polyacetal resin (I) is acopolymer having a melting point of 164 to 172° C.
 7. The polyacetalresin composition according to claim 1, wherein the calcium carbonate(II) is light calcium carbonate.
 8. The polyacetal resin compositionaccording to claim 7, wherein the calcium carbonate (II) has an averageparticle diameter of from 0.1 μm to 1.0 μm.
 9. The polyacetal resincomposition according to claim 7, wherein the calcium carbonate (II) hasa content of particles having a particle diameter of 1 μm or less of 90%or more.
 10. The polyacetal resin composition according to claim 7,wherein the calcium carbonate (II) has a BET specific surface area offrom 10 to 200 m²/g.
 11. The polyacetal resin composition according toclaim 7, wherein the calcium carbonate (II) comprises sphericalparticles, cubic particles, rectangular particles, amorphous particles,or a mixture thereof.
 12. The polyacetal resin composition according toclaim 1, wherein the organic acid (III) is a saturated fatty acid having8 to 36 carbon atoms.
 13. The polyacetal resin composition according toclaim 1, wherein the fatty acid ester (IV) is an ester of a fatty acidhaving 10 to 24 carbon atoms with a monohydric or polyhydric alcoholhaving 2 to 22 carbon atoms.
 14. A polyacetal resin compositioncomprising the polyacetal resin composition according to claim 1 andfurther (V) 0.1 to 10 parts by weight of a polyalkylene glycol per 100parts by weight of the polyacetal resin composition.
 15. The polyacetalresin composition according to claim 14, wherein the polyalkylene glycol(V) is polyethylene glycol or polypropylene glycol.
 16. The polyacetalresin composition according to claim 15, wherein the polyalkylene glycol(V) has a number-average molecular weight of from 10,000 to 45,000.